CN107456879A - Nano silicon/nanofiber water-oil separating composite membrane and preparation method thereof - Google Patents
Nano silicon/nanofiber water-oil separating composite membrane and preparation method thereof Download PDFInfo
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- CN107456879A CN107456879A CN201710833984.5A CN201710833984A CN107456879A CN 107456879 A CN107456879 A CN 107456879A CN 201710833984 A CN201710833984 A CN 201710833984A CN 107456879 A CN107456879 A CN 107456879A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0079—Manufacture of membranes comprising organic and inorganic components
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D17/00—Separation of liquids, not provided for elsewhere, e.g. by thermal diffusion
- B01D17/02—Separation of non-miscible liquids
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/12—Composite membranes; Ultra-thin membranes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/40—Polymers of unsaturated acids or derivatives thereof, e.g. salts, amides, imides, nitriles, anhydrides, esters
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/58—Other polymers having nitrogen in the main chain, with or without oxygen or carbon only
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/72—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, not provided for in a single one of the groups B01D71/46 - B01D71/70 and B01D71/701 - B01D71/702
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/36—Hydrophilic membranes
Abstract
The present invention relates to film field of engineering technology, more particularly to a kind of nano silicon/nanofiber water-oil separating composite membrane and preparation method thereof.The preparation method of the present invention, including step：1) nanosilica solution is prepared：Dissolved after nano-silicon dioxide particle is mixed with water-soluble polymer and obtain nanosilica solution in a solvent；2) nanofiber suspension is prepared：By the nanofiber dispersion after high-speed shearing machine is handled in solvent, nanofiber suspension is obtained；3) nano silicon/nanofiber water-oil separating composite membrane is prepared：Preparation liquid is obtained after nanosilica solution is well mixed with nanofiber suspension, preparation liquid is coated on substrate surface, nano silicon/nanofiber water-oil separating composite membrane is produced after drying.The preparation method of the present invention is simple；Obtained nano silicon/nanofiber water-oil separating composite membrane not only has preferable mechanical strength, and has higher separative efficiency.
Description
Technical field
The present invention relates to film field of engineering technology, more particularly to a kind of nano silicon/nanofiber water-oil separating to answer
Close film and preparation method thereof.
Background technology
Greasy dirts are largely produced in industrial production and daily life, the nowadays environmental improvement of being treated as to oil-polluted water
Matter of utmost importance, at present, the processing to oil-polluted water include oil removal, gas floating and biochemical treatment, rising in recent years using membrane material as
The filter-type oil-water separation method on basis, because it has easy to use, separate many advantages, such as thorough and be widely used.
But existing water-oil separating membrane preparation method is all complex, such as Chinese invention patent (Publication No.
CN104313796B, publication date are on May 11st, 2016), a kind of manufacture method of water-oil separating tunica fibrosa of denomination of invention.Should
Water-oil separationg film be by adjust monomer ratio and control suspension polymerization condition, it is synthetically prepared go out extremely hydrophobic organic polymer
Compound water-oil separating tunica fibrosa.This preparation process includes a systems such as suspension polymerisation, spinning solution control, deaeration, electrostatic spinning
Row processing step, preparation process very complicated, cascading effect is also easy to produce between each step, not being suitable for industrial mass production should
With.China Patent Publication No. is CN 102797197A, and publication date is on November 28th, 2012, a kind of water-oil separating of denomination of invention
The preparation method of filter paper.The preparation method of the oil-water separation filter paper is successively to add tetraethyl orthosilicate and ammoniacal liquor in ethanol to react
Afterwards stand and overnight aging, then will octadecyl trichlorosilane alkane add aging mixed liquor in, washed by magnetic agitation, alcohol, from
After the heart, drying and other steps, the tetrahydrofuran solution preparation that obtained hydrophobic silica particles are dissolved in polystyrene is hydrophobic
Silica/polystyrene/tetrahydrofuran mixed liquor；Filter paper is dipped in above-mentioned mixed liquor, after drying at room temperature or drawn certain
Above-mentioned mixed liquor is uniformly applied to its surface, and oil-water separation filter paper is obtained after drying at room temperature.
Secondly, existing water-oil separationg film manufacturing cost is high, introduced in preparation process heavy metal, fluorochemical or its
Many contingency questions such as his poisonous and harmful element, easy generation environment pollution, it is impossible to large-scale production suitable for industry and make
With.Finally, existing water-oil separating membrane stability is poor, and contamination resistance is bad, and fenestra is easily blocked, it is impossible to repeatedly or long
Time Continuous uses.
The content of the invention
It is an object of the invention to provide a kind of nano silicon/nanofiber water-oil separating composite membrane and its preparation side
Method, its preparation method is simple, low production cost；Obtained nano silicon/nanofiber water-oil separating composite membrane is not only
With preferable oil-water separation, and the particulate contamination in water can also be filtered out.
To achieve the above object, the system of nano silicon/nanofiber water-oil separating composite membrane designed by the present invention
Preparation Method, comprise the following steps：
1) nanosilica solution is prepared
Dissolved after hydrophilic nano silicon dioxide granule is mixed with water-soluble polymer and obtain nano-silica in a solvent
SiClx solution；
2) nanofiber suspension is prepared
Hydrophilic Nanofibrous after high-speed shearing machine is handled is scattered in solvent, obtains nanofiber suspension；
3) nano silicon/nanofiber water-oil separating composite membrane is prepared
Preparation liquid is obtained after nanosilica solution is well mixed with nanofiber suspension, preparation liquid is coated on
Substrate surface, nano silicon/nanofiber water-oil separating composite membrane is produced after drying.
Preferably, the mass ratio of the nano-silicon dioxide particle and water-soluble polymer is 2:8~9:1；Institute
The mass percentage concentration for stating nanofiber in nanofiber suspension is 0.5%~60%；The nanosilica solution with
The mass ratio of nanofiber suspension is 4:6~9:1.
Preferably, in the step 3), nanosilica solution is scattered through high speed with nanofiber suspension
Machine or mulser carry out mixed processing；The preparation liquid is through spraying, scratching or the coating method of spin coating is coated on substrate surface；Institute
It is 1~100 μm to state thickness of the preparation liquid coated on substrate surface, and coating grammes per square metre is 5~50gsm；The temperature of the drying is -10
DEG C~40 DEG C.
Preferably, the water-soluble polymer be polyacrylamide, it is polyvinylpyrrolidone, polyvinyl alcohol, poly-
One kind in ethylene glycol, HPMA, Sodium Polyacrylate and polyacrylic acid；The solvent be alcohols solvent, acids solvent and
At least one of ketones solvent；The Hydrophilic Nanofibrous is hydrophilic homopolymer nanofiber or hydrophilic copolymers
Nanofiber；The base material is that raw material is cotton fiber, polypropylene fibre, pet fiber, polyacrylonitrile
A kind of woven cloth or non-woven cloth in fiber, polyvinyl chloride fibre or Fypro.
Preferably, described hydrophilic homopolymer nanofiber is polyvinyl alcohol nano, polyethylene glycol
Nanofiber, polyacrylamide nano fiber, Sodium Polyacrylate nanofiber or polyacrylic acid nano fiber；The hydrophily is total to
Polymers nanofiber is vinyl alcohol-acrylic copolymer (PVA-co-PAA) nanofiber, PLA (PLA) nanofiber or second
Vinyl pyrrolidone-methylmethacrylate copolymer (PVP-co-PMMA) nanofiber.
Involved reagent material commercially buys gained, wherein nanofiber in addition to nanofiber in the present invention
Nanofiber of the preparation method described in referring to patent CN 105148996A, CN 104014196 B, CN 103884695 A
Preparation method, i.e., using the two kinds of mutual exclusive polymer of thermodynamics abundant melt blendings in twin-screw melt extruder, squeeze
Go out, the polymer melt of blending is extended change in extruder and spinning head by the effect of shearing force and stretching compound force field
Shape, bundles of nanofibers is formed, finally, remove matrix polymer, obtain nanofiber.
The advantage of the invention is that：
(1) being mixed using water-soluble polymer with nano-silicon dioxide particle in the present invention, water-soluble polymer can make
Nano-silicon dioxide particle is bonded on nanofiber, and the group of nano-silicon dioxide particle is avoided while preventing it from coming off
It is poly-；Using alcohols solvent, acids solvent and ketones solvent nano-silicon dioxide particle and nanofiber can be made not to precipitate and energy
Form stable suspension.
(2) in the surface and inside of nano silicon produced by the present invention/nanofiber water-oil separating composite membrane, nanometer
Silicon dioxide granule is uniformly distributed with nanofiber in three-dimensional, and structure and property are stable, and obtained water-oil separating composite membrane has
Higher water-oil separating efficiency.
(3) preparation liquid is coated on substrate surface by the inventive method, on the one hand reduces nanofiber and nano silicon
The usage amount of particle, production cost is reduced, on the other hand adds nano silicon/nanofiber water-oil separating composite membrane
Intensity.
(4) present invention uses hydrophilic nano silicon dioxide granule and hydrophily high polymer nano fiber or hydrophilic polymerized
Thing blend nanofiber, the hydrophily of obtained nano silicon/nanofiber water-oil separating composite membrane are significantly lifted,
Enhance the ability of water-oil separating.Simultaneously because the diameter of nanofiber is minimum so that the aperture of water-oil separating composite membrane is micropore
Rank, the particulate contamination in water can also be filtered out while water-oil separating is realized.
(5) novel nano silica produced by the present invention/nanofiber water-oil separating composite membrane membrane structure is controllable, passes through
The selection of different base fabrics and different nanofibers can prepare hydrophily water-oil separating composite membrane of different sizes.
(6) heavy metal, fluorochemical or other poisonous and harmful elements are not introduced into the inventive method preparation process, it is selected
Reagent and raw material be it is environmentally friendly, will not generation environment pollution etc. contingency question.
Embodiment
To more fully understand the present invention, invention is described in detail below with reference to instantiation.
To solve to exist in existing water-oil separating composite membrane, preparation method is complicated, preparing cost, high, easy generation environment is dirty
The problem of dye, water-oil separating membrane stability difference, the present invention provide a kind of nano silicon/nanofiber water-oil separating composite membrane
And preparation method thereof, the water-oil separating composite membrane is mainly by base material and nanofiber and the nanometer being attached on nanofiber two
Silicon oxide particle forms.The present invention using nanofiber easy entanglement easy film forming the characteristics of, make to be bonded in the parent on nanofiber
The silicon particle of water nano two can be present in the inside and surface of composite membrane, can not only strengthen the stabilization of water-oil separating composite membrane
Property, and can greatly increase the hydrophily of water-oil separating composite membrane and the roughness on film surface, so as to be mixed to profit
Compound carries out more efficiently separation.Below by by specific embodiment come to the present invention nano silicon/Nanowire
The preferred embodiment of dimension water-oil separating composite membrane and preparation method thereof is described in detail.
Embodiment 1
The preparation method of nano silicon/nanofiber water-oil separating composite membrane, comprises the following steps：
1) nanosilica solution is prepared
It is dissolved in after hydrophilic nano silicon dioxide granule is mixed with polyacrylamide in alcohol solvent and obtains nanometer two
Silica solution；Wherein the mass ratio of hydrophilic nano silicon dioxide granule and polyacrylamide is 2:8.
2) nanofiber suspension is prepared
Polyvinyl alcohol (PVA) nanofiber dispersion after high-speed shearing machine is handled in alcohol solvent, is obtained into nanometer
Fibrous suspension；The mass percentage concentration of PVA nanofibers is 0.5% in nanofiber suspension.
3) nano silicon/nanofiber water-oil separating composite membrane is prepared
Nanosilica solution after high speed dispersor is well mixed is obtained into preparation liquid with nanofiber suspension, received
Rice silicon dioxde solution and the mass ratio of nanofiber suspension are 4:6；Coating method of the preparation liquid through spraying is coated on base
Material cotton fiber woven cloth surface, thickness of the preparation liquid coated on substrate surface is 1 μm, and coating grammes per square metre is 5gsm；Produced after drying
Nano silicon/nanofiber water-oil separating composite membrane, dry temperature are -10 DEG C.The measurement of via hole diameter tester understands multiple
The average pore size for closing film is 0.07 μm.
At room temperature, nano silicon made from embodiment 1/nanofiber water-oil separating composite membrane is fixed on gravity
In filter, the mixture of 50ml vegetable oil and 150ml water is poured into filter above film, divided in water added with quality
The nano-titania particle that the size that number is 10% is 50nm, under gravity about after 1min, it was observed that water can be whole
By film, but oil reservoir is trapped within film surface, can not pass through.Used by the oil and aqueous mixtures of water-oil separating composite membrane total organic
The separative efficiency that carbon analyzer detects is 99.91%, understands that 50nm particle concentration is through the measurement of Malvern laser particle analyzer
Zero.Observed after device is placed in into 24h at room temperature, oil reservoir is not over composite membrane.Show the nanometer titanium dioxide that the present embodiment 1 obtains
The oil-water separation of silicon/nanofiber water-oil separating composite membrane is good, and oil reservoir shows nanometer not over composite membrane after 24h
The stability of silica/nanofiber water-oil separating composite membrane is good, and can also filter out the particulate contamination in water.
Embodiment 2
The preparation method of nano silicon/nanofiber water-oil separating composite membrane, comprises the following steps：
1) nanosilica solution is prepared
It is dissolved in acetic acid solvent and is received after hydrophilic nano silicon dioxide granule is mixed with polyvinylpyrrolidone
Rice silicon dioxde solution；Wherein the mass ratio of hydrophilic nano silicon dioxide granule and polyvinylpyrrolidone is 9:1.
2) nanofiber suspension is prepared
Polyethylene glycol (PEG) nanofiber dispersion after high-speed shearing machine is handled in acetic acid solvent, is obtained into nanometer
Fibrous suspension；The mass percentage concentration of PEG nanofibers is 60% in nanofiber suspension.
3) nano silicon/nanofiber water-oil separating composite membrane is prepared
Nanosilica solution is obtained into preparation liquid, nanometer two with nanofiber suspension after mulser is well mixed
Silica solution and the mass ratio of nanofiber suspension are 9:1；Coating method of the preparation liquid through blade coating is coated on polypropylene
The nonwoven fabric surface of fiber, the thickness of nonwoven fabric surface of the preparation liquid coated on polypropylene fibre is 100 μm, coats grammes per square metre
For 50gsm；Nano silicon/nanofiber water-oil separating composite membrane is produced after drying, dry temperature is 40 DEG C.Via hole diameter
Tester measurement understands that the average pore size of composite membrane is 0.065 μm.
At room temperature, nano silicon made from embodiment 2/nanofiber water-oil separating composite membrane is fixed on gravity
In filter, the mixture of 50ml vegetable oil and 150ml water is poured into filter above film, divided in water added with quality
The nano-silicon dioxide particle that the size that number is 10% is 30nm, under gravity about after 3min, it was observed that water can be whole
By film, but oil reservoir is trapped within film surface, can not pass through.Used by the oil and aqueous mixtures of water-oil separating composite membrane total organic
The separative efficiency that carbon analyzer detects is 99.98%, understands that 30nm particle concentration is through the measurement of Malvern laser particle analyzer
Zero.Observed after device is placed in into 36h at room temperature, oil reservoir is not over composite membrane.Show the nanometer titanium dioxide that the present embodiment 2 obtains
The oil-water separation of silicon/nanofiber water-oil separating composite membrane is good, and oil reservoir shows nanometer not over composite membrane after 36h
The stability of silica/nanofiber water-oil separating composite membrane is good, and can also filter out the particulate contamination in water.
Embodiment 3
The preparation method of nano silicon/nanofiber water-oil separating composite membrane, comprises the following steps：
1) nanosilica solution is prepared
Nano-silica is obtained by being dissolved in after hydrophilic nano silicon dioxide granule and polyvinyl alcohol in acetone solvent
SiClx solution；Wherein the mass ratio of hydrophilic nano silicon dioxide granule and polyvinyl alcohol is 1:3.
2) nanofiber suspension is prepared
Polyacrylic acid (PAA) nanofiber dispersion after high-speed shearing machine is handled in methanol solvate, is obtained into nanometer
Fibrous suspension；The mass percentage concentration of PAA nanofibers is 10% in the nanofiber suspension.
3) nano silicon/nanofiber water-oil separating composite membrane is prepared
Nanosilica solution after high speed dispersor is well mixed is obtained into preparation liquid with nanofiber suspension, received
Rice silicon dioxde solution and the mass ratio of nanofiber suspension are 1:1；By the spin-coated coating method of preparation liquid coated on poly-
Ethylene glycol terephthalate fiber non-woven surface, preparation liquid are non-woven coated on pet fiber
The thickness on cloth surface is 20 μm, and coating grammes per square metre is 15gsm；Nano silicon/nanofiber water-oil separating is produced after drying to answer
Film is closed, dry temperature is 15 DEG C.The measurement of via hole diameter tester understands that the average pore size of composite membrane is 0.075 μm.
At room temperature, nano silicon made from embodiment 3/nanofiber water-oil separating composite membrane is fixed on gravity
In filter, the mixture of 50ml vegetable oil and 150ml water is poured into filter above film, divided in water added with quality
The nano alumina particles that the size that number is 10% is 20nm, under gravity about after 3.5min, it was observed that water can be whole
By film, but oil reservoir is trapped within film surface, can not pass through.Used by the oil and aqueous mixtures of water-oil separating composite membrane total organic
The separative efficiency that carbon analyzer detects is 99.95%, understands that 20nm particle concentration is through the measurement of Malvern laser particle analyzer
Zero.Observed after device is placed in into 48h at room temperature, oil reservoir is not over composite membrane.Show the nanometer titanium dioxide that the present embodiment 3 obtains
The oil-water separation of silicon/nanofiber water-oil separating composite membrane is good, and oil reservoir shows nanometer not over composite membrane after 48h
The stability of silica/nanofiber water-oil separating composite membrane is good.And the particulate contamination in water can also be filtered out.
Embodiment 4
The preparation method of nano silicon/nanofiber water-oil separating composite membrane, comprises the following steps：
1) nanosilica solution is prepared
It is dissolved in after hydrophilic nano silicon dioxide granule is mixed with polyethylene glycol in solvent oxalic acid solvent and obtains nanometer
Silicon dioxde solution；Wherein the mass ratio of hydrophilic nano silicon dioxide granule and polyethylene glycol is 2:5.
2) nanofiber suspension is prepared
By vinyl alcohol-acrylic copolymer (PVA-co-PAA) nanofiber dispersion after high-speed shearing machine is handled in molten
In agent, nanofiber suspension is obtained；The mass percentage concentration of PVA-co-PAA nanofibers in the nanofiber suspension
For 41%.
3) nano silicon/nanofiber water-oil separating composite membrane is prepared
Nanosilica solution is obtained into preparation liquid, nanometer two with nanofiber suspension after mulser is well mixed
Silica solution and the mass ratio of nanofiber suspension are 4:1；The spin-coated coating method of preparation liquid is coated on polypropylene
Nitrile fiber non-woven surface, thickness of the preparation liquid coated on polyacrylonitrile fibre nonwoven fabric surface are 45 μm, coat grammes per square metre
For 35gsm；Nano silicon/nanofiber water-oil separating composite membrane is produced after drying, dry temperature is 27 DEG C.Via hole diameter
Tester measurement understands that the average pore size of composite membrane is 0.072 μm.
At room temperature, nano silicon made from embodiment 4/nanofiber water-oil separating composite membrane is fixed on gravity
In filter, the mixture of 50ml vegetable oil and 150ml water is poured into filter above film, divided in water added with quality
The nano-titania particle that the size that number is 10% is 100nm, under gravity about after 3min, it was observed that water can be whole
By film, but oil reservoir is trapped within film surface, can not pass through.Used by the oil and aqueous mixtures of water-oil separating composite membrane total organic
The separative efficiency that carbon analyzer detects is 99.96%, understands that 100nm particle concentration is through the measurement of Malvern laser particle analyzer
Zero.Observed after device is placed in into 72h at room temperature, oil reservoir is not over composite membrane.Show the nanometer titanium dioxide that the present embodiment 4 obtains
The oil-water separation of silicon/nanofiber water-oil separating composite membrane is good, and oil reservoir shows nanometer not over composite membrane after 72h
The stability of silica/nanofiber water-oil separating composite membrane is good, and can also filter out the particulate contamination in water.
Embodiment 5
The preparation method of nano silicon/nanofiber water-oil separating composite membrane, comprises the following steps：
1) nanosilica solution is prepared
It is dissolved in after hydrophilic nano silicon dioxide granule is mixed with HPMA in cyclohexanone solvent and obtains nanometer
Silicon dioxde solution；Wherein the mass ratio of hydrophilic nano silicon dioxide granule and polyacrylic acid is 4:5.
2) nanofiber suspension is prepared
Nanofiber PLA (PLA) nanofiber dispersion after high-speed shearing machine is handled in solvent, is received
Rice fibrous suspension；The mass percentage concentration of PLA (PLA) nanofiber is 50% in the nanofiber suspension.
3) nano silicon/nanofiber water-oil separating composite membrane is prepared
Nanosilica solution is obtained into preparation liquid, nanometer two with nanofiber suspension after mulser is well mixed
Silica solution and the mass ratio of nanofiber suspension are 5:1；Coating method of the preparation liquid through spraying is coated on polychlorostyrene second
Alkene fiber non-woven surface, thickness of the preparation liquid coated on substrate surface is 90 μm, and coating grammes per square metre is 45gsm；After drying i.e.
Nano silicon/nanofiber water-oil separating composite membrane is obtained, dry temperature is 35 DEG C.The measurement of via hole diameter tester understands multiple
The average pore size for closing film is 0.079 μm.
At room temperature, nano silicon made from embodiment 5/nanofiber water-oil separating composite membrane is fixed on gravity
In filter, the mixture of 50ml vegetable oil and 150ml water is poured into filter above film, divided in water added with quality
The nano-silicon dioxide particle that the size that number is 10% is 15nm, under gravity about after 4min, it was observed that water can be whole
By film, but oil reservoir is trapped within film surface, can not pass through.Used by the oil and aqueous mixtures of water-oil separating composite membrane total organic
The separative efficiency that carbon analyzer detects is 99.93%, understands that 15nm particle concentration is through the measurement of Malvern laser particle analyzer
Zero.Observed after device is placed in into 84h at room temperature, oil reservoir is not over composite membrane.Show the nanometer titanium dioxide that the present embodiment 5 obtains
The oil-water separation of silicon/nanofiber water-oil separating composite membrane is good, and oil reservoir shows nanometer not over composite membrane after 84h
The stability of silica/nanofiber water-oil separating composite membrane is good, and can also filter out the particulate contamination in water.
Embodiment 6
The preparation method of nano silicon/nanofiber water-oil separating composite membrane, comprises the following steps：
1) nanosilica solution is prepared
It is dissolved in after hydrophilic nano silicon dioxide granule is mixed with Sodium Polyacrylate in alcohol solvent and obtains nanometer two
Silica solution；Wherein the mass ratio of hydrophilic nano silicon dioxide granule and polyacrylamide is 3:1.
2) nanofiber suspension is prepared
By the Sodium Polyacrylate nanofiber dispersion after high-speed shearing machine is handled in solvent, nanofiber suspension is obtained
Liquid；The mass percentage concentration of Sodium Polyacrylate nanofiber is 2% in the nanofiber suspension.
3) nano silicon/nanofiber water-oil separating composite membrane is prepared
Nanosilica solution after high speed dispersor is well mixed is obtained into preparation liquid with nanofiber suspension, received
Rice silicon dioxde solution and the mass ratio of nanofiber suspension are 6:1；The coating method of preparation liquid spin coating is coated on polyamides
The woven cloth surface of amine fiber, the thickness on woven cloth surface of the preparation liquid coated on Fypro is 90 μm, and coating grammes per square metre is
45gsm；Nano silicon/nanofiber water-oil separating composite membrane is produced after drying, dry temperature is 38 DEG C.Via hole diameter is surveyed
Try instrument measurement and understand that the average pore size of composite membrane is 0.067 μm.
At room temperature, nano silicon made from embodiment 6/nanofiber water-oil separating composite membrane is fixed on gravity
In filter, the mixture of 50ml vegetable oil and 150ml water is poured into filter above film, divided in water added with quality
The nano-silicon dioxide particle that the size that number is 10% is 40nm, under gravity about after 5min, it was observed that water can be whole
By film, but oil reservoir is trapped within film surface, can not pass through.Used by the oil and aqueous mixtures of water-oil separating composite membrane total organic
The separative efficiency that carbon analyzer detects is 99.97%, understands that 40nm particle concentration is through the measurement of Malvern laser particle analyzer
Zero.Observed after device is placed in into 96h at room temperature, oil reservoir is not over composite membrane.Show the nanometer titanium dioxide that the present embodiment 6 obtains
The oil-water separation of silicon/nanofiber water-oil separating composite membrane is good, and oil reservoir shows nanometer not over composite membrane after 96h
The stability of silica/nanofiber water-oil separating composite membrane is good, and can also filter out the particulate contamination in water.
Embodiment 7
The preparation method of nano silicon/nanofiber water-oil separating composite membrane, comprises the following steps：
1) nanosilica solution is prepared
The mixed solvent of ethanol and acetic acid is dissolved in after hydrophilic nano silicon dioxide granule is mixed with polyacrylamide
In obtain nanosilica solution；Wherein the mass ratio of hydrophilic nano silicon dioxide granule and polyacrylamide is 5:1；Second
The volume ratio of the in the mixed solvent ethanol and acetic acid of alcohol and acetic acid is 1:1.
2) nanofiber suspension is prepared
By the vinyl pyrrolidone after high-speed shearing machine is handled-methylmethacrylate copolymer (PVP-co-
PMMA) nanofiber dispersion obtains nanofiber suspension in the in the mixed solvent of ethanol and acetic acid；In nanofiber suspension
The mass percentage concentration of PVP-co-PMMA nanofibers is 30%.
3) nano silicon/nanofiber water-oil separating composite membrane is prepared
Nanosilica solution after high speed dispersor is well mixed is obtained into preparation liquid with nanofiber suspension, received
Rice silicon dioxde solution and the mass ratio of nanofiber suspension are 8:1；The coating method of preparation liquid blade coating is fine coated on cotton
Nonwoven fabric surface is tieed up, thickness of the preparation liquid coated on cotton fiber nonwoven fabric surface is 5 μm, and coating grammes per square metre is 7gsm；Dry
After produce nano silicon/nanofiber water-oil separating composite membrane, dry temperature is 20 DEG C.
Embodiment 8
The preparation method of nano silicon/nanofiber water-oil separating composite membrane, comprises the following steps：
1) nanosilica solution is prepared
It is dissolved in after hydrophilic nano silicon dioxide granule is mixed with polyacrylic acid in alcohol solvent and obtains nano-silica
SiClx solution；Wherein the mass ratio of hydrophobic nano-silica particle and polyacrylamide is 1:1.
2) nanofiber suspension is prepared
Polyacrylamide nano fiber after high-speed shearing machine is handled is scattered in solvent, obtains nanofiber suspension
Liquid；The mass percentage concentration of polyacrylamide nano fiber is 20% in the nanofiber suspension.
3) nano silicon/nanofiber water-oil separating composite membrane is prepared
Nanosilica solution is obtained into preparation liquid, nanometer two with nanofiber suspension after mulser is well mixed
Silica solution and the mass ratio of nanofiber suspension are 2:1；Coating method of the preparation liquid through spraying is coated on polypropylene
Fibre knitting cloth surface, thickness of the preparation liquid coated on polypropylene fibre woven cloth surface is 20 μm, and coating grammes per square metre is 10gsm；
Nano silicon/nanofiber water-oil separating composite membrane is produced after drying, dry temperature is 10 DEG C.
Embodiment described above only expresses 8 kinds of embodiments of the present invention, and its description is more specific and detailed, but not
Therefore the limitation to the scope of the claims of the present invention can be interpreted as.It should be pointed out that come for one of ordinary skill in the art
Say, without departing from the inventive concept of the premise, various modifications and improvements can be made, these belong to the protection of the present invention
Scope.Therefore, the protection domain of patent of the present invention should be determined by the appended claims.
Claims (6)
- A kind of 1. preparation method of nano silicon/nanofiber water-oil separating composite membrane, it is characterised in that：Including following step Suddenly：1) nanosilica solution is preparedDissolved after hydrophilic nano silicon dioxide granule is mixed with water-soluble polymer and obtain nano silicon in a solvent Solution；2) nanofiber suspension is preparedHydrophilic Nanofibrous after high-speed shearing machine is handled is scattered in solvent, obtains nanofiber suspension；3) nano silicon/nanofiber water-oil separating composite membrane is preparedPreparation liquid is obtained after nanosilica solution is well mixed with nanofiber suspension, preparation liquid is coated on base material Surface, nano silicon/nanofiber water-oil separating composite membrane is produced after drying.
- 2. the preparation method of nano silicon according to claim 1/nanofiber water-oil separating composite membrane, its feature It is：The mass ratio of the nano-silicon dioxide particle and water-soluble polymer is 2:8~9:1；The nanofiber suspension The mass percentage concentration of middle nanofiber is 0.5%~60%；The nanosilica solution and nanofiber suspension Mass ratio is 4:6~9:1.
- 3. the preparation method of nano silicon according to claim 1/nanofiber water-oil separating composite membrane, its feature It is：In the step 3), nanosilica solution is mixed with nanofiber suspension through high speed dispersor or mulser Conjunction is handled；The preparation liquid is through spraying, scratching or the coating method of spin coating is coated on substrate surface；The preparation liquid is coated on base The thickness on material surface is 1~100 μm, and coating grammes per square metre is 5~50gsm；The temperature of the drying is -10 DEG C~40 DEG C.
- 4. the preparation method of nano silicon according to claim 2/nanofiber water-oil separating composite membrane, its feature It is：The water-soluble polymer is polyacrylamide, polyvinylpyrrolidone, polyvinyl alcohol, polyethylene glycol, poly One kind in acid anhydride, Sodium Polyacrylate and polyacrylic acid；The solvent be alcohols solvent, acids solvent and ketones solvent at least It is a kind of；The Hydrophilic Nanofibrous is hydrophilic homopolymer nanofiber or hydrophilic copolymers nanofiber；The base Material is that raw material is cotton fiber, polypropylene fibre, pet fiber, polyacrylonitrile fibre, polyvinyl chloride fibre Dimension or a kind of woven cloth or non-woven cloth in Fypro.
- 5. the preparation method of nano silicon according to claim 4/nanofiber water-oil separating composite membrane, its feature It is：Described hydrophilic homopolymer nanofiber is polyvinyl alcohol nano, polyethylene glycol nanofiber, polyacrylamide Amine nanofiber, Sodium Polyacrylate nanofiber or polyacrylic acid nano fiber；The hydrophilic copolymers nanofiber is second Enol-acrylic copolymer nanofiber, polylactic acid nano fiber or vinyl pyrrolidone-methyl methacrylate copolymer Thing nanofiber.
- A kind of 6. nano silicon/nanofiber water-oil separating composite membrane, it is characterised in that：It is by Claims 1 to 5 The preparation method of nano silicon/nanofiber water-oil separating composite membrane described in any one is prepared.
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